Carrier Screening Controls Transport in Conjugated Polymers at High Doping Concentrations.

Transport properties of doped conjugated polymers (CPs) have been widely analyzed with the Gaussian disorder model (GDM) in conjunction with hopping transport between localized states. These models reveal that even in highly doped CPs, a majority of carriers are still localized because dielectric permittivity of CPs is well below that of inorganic materials, making Coulomb interactions between carriers and dopant counterions much more pronounced. However, previous studies within the GDM did not consider the role of screening the dielectric interactions by carriers. Here we implement carrier screening in the Debye-Hückel formalism in our calculations of dopant-induced energetic disorder, which modifies the Gaussian density of states (DOS). Then we solve the Pauli master equation using Miller-Abrahams hopping rates with states from the resulting screened DOS to obtain conductivity and Seebeck coefficient across a broad range of carrier concentrations and compare them to measurements. Our results show that screening has significant impact on the shape of the DOS and consequently on carrier transport, particularly at high doping. We prove that the slope of Seebeck coefficient versus electric conductivity, which was previously thought to be universal, is impacted by screening and decreases for systems with small dopant-carrier separation, explaining our measurements. We also show that thermoelectric power factor is underestimated by a factor of ∼10 at higher doping concentrations if screening is neglected. We conclude that carrier screening plays a crucial role in curtailing dopant-induced energetic disorder, particularly at high carrier concentrations.

Giant Isotope Effect of Thermal Conductivity in Silicon Nanowires.

Isotopically purified semiconductors potentially dissipate heat better than their natural, isotopically mixed counterparts as they have higher thermal conductivity (κ). But the benefit is low for Si at room temperature, amounting to only ∼10% higher κ for bulk ^{28}Si than for bulk natural Si (^{nat}Si). We show that in stark contrast to this bulk behavior, ^{28}Si (99.92% enriched) nanowires have up to 150% higher κ than ^{nat}Si nanowires with similar diameters and surface morphology. Using a first-principles phonon dispersion model, this giant isotope effect is attributed to a mutual enhancement of isotope scattering and surface scattering of phonons in ^{nat}Si nanowires, correlated via transmission of phonons to the native amorphous SiO_{2} shell. The Letter discovers the strongest isotope effect of κ at room temperature among all materials reported to date and inspires potential applications of isotopically enriched semiconductors in microelectronics.

Thermal boundary conductance of monolayer beyond-graphene two-dimensional materials on SiO2and GaN.

Two-dimensional (2D) materials have emerged as a platform for a broad array of future nanoelectronic devices. Here we use first-principles calculations and phonon interface transport modeling to calculate the temperature-dependent thermal boundary conductance (TBC) in single layers of beyond-graphene 2D materials silicene, hBN, boron arsenide (BAs), and blue and black phosphorene (BP) on amorphous SiO2and crystalline GaN substrates. Our results show that for 2D/3D systems, the room temperature TBC can span a wide range from  7 to 70 MW m-2K-1 with the lowest being for BP and highest for hBN. We also show that 2D/3D TBC has a strong temperature dependence that can be alleviated by encapsulating the 2D/3D stack. Upon encapsulation with AlOx, the TBC of several beyond-graphene 2D materials can match or exceed reported values for graphene and numerous transition-metal dichalcogendies which are in the range of 15-40 MW m-2K-1. We also compute the room temperature TBC as a function of van der Waals spring coupling (Ka) where the TBC falls in the range of 50-150 MW m-2K-1 at coupling strengths ofKa = 2-4 N m-1 for silicene, BAs, and blue phosphorene. We further identify group III-V materials with ultra-soft flexural branches as being promising 2D materials for thermal isolation and energy scavenging applications when matched with crystalline substrates.

Direct Growth of High Mobility and Low-Noise Lateral MoS2 -Graphene Heterostructure Electronics.

Reliable fabrication of lateral interfaces between conducting and semiconducting 2D materials is considered a major technological advancement for the next generation of highly packed all-2D electronic circuitry. This study employs seed-free consecutive chemical vapor deposition processes to synthesize high-quality lateral MoS2 -graphene heterostructures and comprehensively investigated their electronic properties through a combination of various experimental techniques and theoretical modeling. These results show that the MoS2 -graphene devices exhibit an order of magnitude higher mobility and lower noise metrics compared to conventional MoS2 -metal devices as a result of energy band rearrangement and smaller Schottky barrier height at the contacts. These findings suggest that MoS2 -graphene in-plane heterostructures are promising materials for the scale-up of all-2D circuitry with superlative electrical performance.

Interface thermal conductance of van der Waals monolayers on amorphous substrates.

Heterostructures based on atomic monolayers are emerging as leading materials for future energy efficient and multifunctional electronics. Due to the single atom thickness of monolayers, their properties are strongly affected by interactions with the external environment. We develop a model for interface thermal conductance (ITC) in an atomic monolayer van der Waals bonded to a disordered substrate. Graphene on SiO2 is initially used in our model and contrasted against available experimental data; the model is then applied to monolayer molybdenum disulfide (MoS2) on SiO2 substrate. Our findings show the dominant carrier of heat in both graphene and MoS2 in the cross-plane direction is the flexural (ZA) phonon mode, owing to the large overlap between graphene ZA and substrate vibrational density of states. The rate of phonon transfer across the interface depends quadratically on the substrate coupling constant K a , but this interaction also causes a lifting of the lowest flexural phonon modes. As a result, ITC depends roughly linearly on the strength of the coupling between a monolayer and its substrate. We conclude that, in both graphene and MoS2 on SiO2, substrate adhesion plays a strong role in determining ITC, requiring further study of substrate coupling in TMDCs.

Bimodal Phonon Scattering in Graphene Grain Boundaries.

Graphene has served as the model 2D system for over a decade, and the effects of grain boundaries (GBs) on its electrical and mechanical properties are very well investigated. However, no direct measurement of the correlation between thermal transport and graphene GBs has been reported. Here, we report a simultaneous comparison of thermal transport in supported single crystalline graphene to thermal transport across an individual graphene GB. Our experiments show that thermal conductance (per unit area) through an isolated GB can be up to an order of magnitude lower than the theoretically anticipated values. Our measurements are supported by Boltzmann transport modeling which uncovers a new bimodal phonon scattering phenomenon initiated by the GB structure. In this novel scattering mechanism, boundary roughness scattering dominates the phonon transport in low-mismatch GBs, while for higher mismatch angles there is an additional resistance caused by the formation of a disordered region at the GB. Nonequilibrium molecular dynamics simulations verify that the amount of disorder in the GB region is the determining factor in impeding thermal transport across GBs.

Phonon-assisted field emission in silicon nanomembranes for time-of-flight mass spectrometry of proteins.

Time-of-flight (TOF) mass spectrometry has been considered as the method of choice for mass analysis of large intact biomolecules, which are ionized in low charge states by matrix-assisted-laser-desorption/ionization (MALDI). However, it remains predominantly restricted to the mass analysis of biomolecules with a mass below about 50,000 Da. This limitation mainly stems from the fact that the sensitivity of the standard detectors decreases with increasing ion mass. We describe here a new principle for ion detection in TOF mass spectrometry, which is based upon suspended silicon nanomembranes. Impinging ion packets on one side of the suspended silicon nanomembrane generate nonequilibrium phonons, which propagate quasi-diffusively and deliver thermal energy to electrons within the silicon nanomembrane. This enhances electron emission from the nanomembrane surface with an electric field applied to it. The nonequilibrium phonon-assisted field emission in the suspended nanomembrane connected to an effective cooling of the nanomembrane via field emission allows mass analysis of megadalton ions with high mass resolution at room temperature. The high resolution of the detector will give better insight into high mass proteins and their functions.

Thermally Driven Field Emission from Zinc Oxide Wires on a Nanomembrane Used as a Detector for Time-of-Flight Mass Spectrometry.

Mass spectrometry is a crucial technology in numerous applications, but it places stringent requirements on the detector to achieve high resolution across a broad spectrum of ion masses. Low-dimensional nanostructures offer opportunities to tailor properties and achieve performance not reachable in bulk materials. Here, an array of sharp zinc oxide wires was directly grown on a 30 nm thin, free-standing silicon nitride nanomembrane to enhance its field emission (FE). The nanomembrane was subsequently used as a matrix-assisted laser desorption/ionization time-of-flight mass spectrometry detector. When ionized biomolecules impinge on the backside of the surface-modified nanomembrane, the current-emitted from the wires on the membrane's front side-is amplified by the supplied thermal energy, which allows for the detection of the ions. An extensive simulation framework was developed based on a combination of lateral heat diffusion in the nanomembrane, heat diffusion along the wires, and FE, including Schottky barrier lowering, to investigate the impact of wire length and diameter on the FE. Our theoretical model suggests a significant improvement in the overall FE response of the nanomembrane by growing wires on top. Specifically, long thin wires are ideal to enhance the magnitude of the FE signal and to shorten its duration for the fastest response simultaneously, which could facilitate the future application of detectors in mass spectrometry with properties improved by low-dimensional nanostructures.

In-plane thermoelectric properties of graphene/xBN/graphene van der Waals heterostructures.

2D materials have attracted broad attention from researchers for their unique electronic properties, which may be been further enhanced by combining 2D layers into vertically stacked van der Waals heterostructures (vdWHs). Among the superlative properties of 2D systems, thermoelectric (TE) energy conversion promises to enable targeted energy conversion, localized thermal management, and thermal sensing. However, TE conversion efficiency remains limited by the inherent tradeoff between conductivity and thermopower. In this paper, we use first-principles calculation to study graphene-based vdWHs composed of graphene layers and hexagonal boron nitride (h-BN). We compute the electronic band structures of heterostructured systems using Quantum Espresso and their TE properties using BoltzTrap2. Our results have shown that stacking layers of these 2D materials opens a bandgap, increasing it with the number of h-BN interlayers, which significantly improves the power factor (PF). We predict a PF of ∼1.0 × 1011W K-2m s for the vdWHs, nearly double compared to 5 × 1010W K-2m s that we obtained for single-layer graphene. This study gives important information on the effect of stacking layers of 2D materials and points toward new avenues to optimize the TE properties of vdWHs.

Reduced thermal conductivity in nanoengineered rough Ge and GaAs nanowires.

We model and compare the thermal conductivity of rough semiconductor nanowires (NWs) of Si, Ge, and GaAs for thermoelectric devices. On the basis of full phonon dispersion relations, the effect of NW surface roughness on thermal conductivity is derived from perturbation theory and appears as an efficient way to scatter phonons in Si, Ge, and GaAs NWs with diameter D < 200 nm. For small diameters and large root-mean-square roughness Delta, thermal conductivity is limited by surface asperities and varies quadratically as (D/Delta)(2). At room temperature, our model previously agreed with experimental observations of thermal conductivity down to 2 W m(-1) K(-1) in rough 56 nm Si NWs with Delta = 3 nm. In comparison to Si, we predict here remarkably low thermal conductivity in Ge and GaAs NWs of 0.1 and 0.4 W m(-1) K(-1), respectively, at similar roughness and diameter.

Raising Dielectric Permittivity Mitigates Dopant-Induced Disorder in Conjugated Polymers.

Conjugated polymers need to be doped to increase charge carrier density and reach the electrical conductivity necessary for electronic and energy applications. While doping increases carrier density, Coulomb interactions between the dopant molecules and the localized carriers are poorly screened, causing broadening and a heavy tail in the electronic density-of-states (DOS). The authors examine the effects of dopant-induced disorder on two complimentary charge transport properties of semiconducting polymers, the Seebeck coefficient and electrical conductivity, and demonstrate a way to mitigate them. Their simulations, based on a modified Gaussian disorder model with Miller-Abrahams hopping rates, show that dopant-induced broadening of the DOS negatively impacts the Seebeck coefficient versus electrical conductivity trade-off curve. Increasing the dielectric permittivity of the polymer mitigates dopant-carrier Coulomb interactions and improves charge transport, evidenced by simultaneous increases in conductivity and the Seebeck coefficient. They verified this increase experimentally in iodine-doped P3HT and P3HT blended with barium titanate (BaTiO3 ) nanoparticles. The addition of 2% w/w BaTiO3 nanoparticles increased conductivity and Seebeck across a broad range of doping, resulting in a fourfold increase in power factor. Thus, these results show a promising path forward to reduce the dopant-charge carrier Coulomb interactions and mitigate their adverse impact on charge transport.

Current Rerouting Improves Heat Removal in Few-Layer WSe2 Devices.

Few-layer (FL) transition-metal dichalcogenides have drawn attention for nanoelectronics applications due to their improved mobility, owing to the partial screening of charged impurities at the oxide interface. However, under realistic operating conditions, dissipation leads to self-heating, which is detrimental to electronic and thermal properties. We fabricated a series of FL-WSe2 devices and measured their I-V characteristics, while their temperatures were quantified by Raman thermometry and simulated from first principles. Our tightly integrated electrothermal study shows that Joule heating leads to a significant layer-dependent temperature rise, which affects mobility and alters the flow of current through the stack. This causes the temperatures in the top layers to increase dramatically, degrading their mobility and causing the current to reroute to the bottom of the FL stack where thermal conductance is higher. We discover that this current rerouting phenomenon improves heat removal because the current flows through layers closer to the substrate, limiting the severity of self-heating and its impact on carrier mobility. We also observe significant lateral heat removal via the contacts because of longer thermal healing length in the top layers and explore the optimum number of layers to maximize mobility in FL devices. Our study will impact future device designs and lead to further improvements in thermal management in van der Waals (vdW)-based devices.

Effects of Disorder on Thermoelectric Properties of Semiconducting Polymers.

Organic materials have attracted recent interest as thermoelectric (TE) converters due to their low cost and ease of fabrication. We examine the effects of disorder on the TE properties of semiconducting polymers based on the Gaussian disorder model (GDM) for site energies while employing Pauli's master equation approach to model hopping between localized sites. Our model is in good agreement with experimental results and a useful tool to study hopping transport. We show that stronger overlap between sites can improve the electrical conductivity without adversely affecting the Seebeck coefficient. We find that positional disorder aids the formation of new conduction paths with an increased probability of carriers in high energy sites, leading to an increase in electrical conductivity while leaving the Seebeck unchanged. On the other hand, energetic disorder leads to increased energy gaps between sites, hindering transport. This adversely affects conductivity while only slightly increasing Seebeck and results in lower TE power factors. Furthermore, positional correlation primarily affects conductivity, while correlation in site energies has no effect on TE properties of polymers. Our results also show that the Lorenz number increases with Seebeck coefficient, largely deviating from the Sommerfeld value, in agreement with experiments and in contrast to band conductors. We conclude that reducing energetic disorder and positional correlation, while increasing positional disorder can lead to higher TE power factors.

Resonant Tunneling Induced Enhancement of Electron Field Emission by Ultra-Thin Coatings.

The emission of electrons from the surface of a material into vacuum depends strongly on the material's work function, temperature, and the intensity of electric field. The combined effects of these give rise to a multitude of related phenomena, including Fowler-Nordheim tunneling and Schottky emission, which, in turn, enable several families of devices, ranging from vacuum tubes, to Schottky diodes, and thermionic energy converters. More recently, nanomembrane-based detectors have found applications in high-resolution mass spectrometry measurements in proteomics. Progress in all the aforementioned applications critically depends on discovering materials with effective low surface work functions. We show that a few atomic layer deposition (ALD) cycles of zinc oxide onto suspended diamond nanomembranes, strongly reduces the threshold voltage for the onset of electron field emission which is captured by resonant tunneling from the ZnO layer. Solving the Schroedinger equation, we obtain an electrical field- and thickness-dependent population of the lowest few subbands in the thin ZnO layer, which results in a minimum in the threshold voltage at a thickness of 1.08 nm being in agreement with the experimentally determined value. We conclude that resonant tunneling enables cost-effective ALD coatings that lower the effective work function and enhance field emission from the device.

Tuning charge transport dynamics via clustering of doping in organic semiconductor thin films.

A significant challenge in the rational design of organic thermoelectric materials is to realize simultaneously high electrical conductivity and high induced-voltage in response to a thermal gradient, which is represented by the Seebeck coefficient. Conventional wisdom posits that the polymer alone dictates thermoelectric efficiency. Herein, we show that doping - in particular, clustering of dopants within conjugated polymer films - has a profound and predictable influence on their thermoelectric properties. We correlate Seebeck coefficient and electrical conductivity of iodine-doped poly(3-hexylthiophene) and poly[2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-3,6-diyl)-alt-(2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] films with Kelvin probe force microscopy to highlight the role of the spatial distribution of dopants in determining overall charge transport. We fit the experimental data to a phonon-assisted hopping model and found that the distribution of dopants alters the distribution of the density of states and the Kang-Snyder transport parameter. These results highlight the importance of controlling dopant distribution within conjugated polymer films for thermoelectric and other electronic applications.

Thermoelectric properties of periodic quantum structures in the Wigner-Rode formalism.

Improving the thermoelectric Seebeck coefficient, while simultaneously reducing thermal conductivity, is required in order to boost thermoelectric (TE) figure of merit (ZT). A common approach to improve the Seebeck coefficient is electron filtering where 'cold' (low energy) electrons are restricted from participating in transport by an energy barrier (Kim and Lundstrom 2011 J. Appl. Phys. 110 034511, Zide et al 2010 J. Appl. Phys. 108 123702). However, the impact of electron tunneling through thin barriers and resonant states on TE properties has been given less attention, despite the widespread use of quantum wells and superlattices (SLs) in TE applications. In our work, we develop a comprehensive transport model using the Wigner-Rode formalism. We include the full electronic bandstructure and all the relevant scattering mechanisms, allowing us to simulate both energy relaxation and quantum effects from periodic potential barriers. We study the impact of barrier shape on TE performance and find that tall, sharp barriers with small period lengths lead to the largest increase in both Seebeck coefficient and conductivity, thus boosting power factor and TE efficiency. Our findings are robust against additional elastic scattering such as atomic-scale roughness at side-walls of SL nanowires.

Power Dissipation of WSe2 Field-Effect Transistors Probed by Low-Frequency Raman Thermometry.

The ongoing shrinkage in the size of two-dimensional (2D) electronic circuitry results in high power densities during device operation, which could cause a significant temperature rise within 2D channels. One challenge in Raman thermometry of 2D materials is that the commonly used high-frequency modes do not precisely represent the temperature rise in some 2D materials because of peak broadening and intensity weakening at elevated temperatures. In this work, we show that a low-frequency E2g2 shear mode can be used to accurately extract temperature and measure thermal boundary conductance (TBC) in back-gated tungsten diselenide (WSe2) field-effect transistors, whereas the high-frequency peaks (E2g1 and A1g) fail to provide reliable thermal information. Our calculations indicate that the broadening of high-frequency Raman-active modes is primarily driven by anharmonic decay into pairs of longitudinal acoustic phonons, resulting in a weak coupling with out-of-plane flexural acoustic phonons that are responsible for the heat transfer to the substrate. We found that the TBC at the interface of WSe2 and Si/SiO2 substrate is ∼16 MW/m2 K, depends on the number of WSe2 layers, and peaks for 3-4 layer stacks. Furthermore, the TBC to the substrate is the highest from the layers closest to it, with each additional layer adding thermal resistance. We conclude that the location where heat dissipated in a multilayer stack is as important to device reliability as the total TBC.

Enhanced Thermal Boundary Conductance in Few-Layer Ti3 C2 MXene with Encapsulation.

Van der Waals interactions in 2D materials have enabled the realization of nanoelectronics with high-density vertical integration. Yet, poor energy transport through such 2D-2D and 2D-3D interfaces can limit a device's performance due to overheating. One long-standing question in the field is how different encapsulating layers (e.g., contact metals or gate oxides) contribute to the thermal transport at the interface of 2D materials with their 3D substrates. Here, a novel self-heating/self-sensing electrical thermometry platform is developed based on atomically thin, metallic Ti3 C2 MXene sheets, which enables experimental investigation of the thermal transport at a Ti3 C2 /SiO2 interface, with and without an aluminum oxide (AlOx ) encapsulating layer. It is found that at room temperature, the thermal boundary conductance (TBC) increases from 10.8 to 19.5 MW m-2 K-1 upon AlOx encapsulation. Boltzmann transport modeling reveals that the TBC can be understood as a series combination of an external resistance between the MXene and the substrate, due to the coupling of low-frequency flexural acoustic (ZA) phonons to substrate modes, and an internal resistance between ZA and in-plane phonon modes. It is revealed that internal resistance is a bottle-neck to heat removal and that encapsulation speeds up the heat transfer into low-frequency ZA modes and reduces their depopulation, thus increasing the effective TBC.

Impact of Mismatch Angle on Electronic Transport Across Grain Boundaries and Interfaces in 2D Materials.

We study the impact of grain boundaries (GB) and misorientation angles between grains on electronic transport in 2-dimensional materials. Here we have developed a numerical model based on the first-principles electronic bandstructure calculations in conjunction with a method which computes electron transmission coefficients from simultaneous conservation of energy and momentum at the interface to essentially evaluate GB/interface resistance in a Landauer formalism. We find that the resistance across graphene GBs vary over a wide range depending on misorientation angles and type of GBs, starting from 53 Ω µm for low-mismatch angles in twin (symmetric) GBs to about 1020 Ω µm for 21° mismatch in tilt (asymmetric) GBs. On the other hand, misorientation angles have weak influence on the resistance across MoS2 GBs, ranging from about 130 Ω µm for low mismatch angles to about 6000 Ω µm for 21°. The interface resistance across graphene-MoS2 heterojunctions also exhibits a strong dependence on misorientation angles with resistance values ranging from about 100 Ω µm for low-mismatch angles in Class-I (symmetric) interfaces to 1015 Ω µm for 14° mismatch in Class-II (asymmetric) interfaces. Overall, symmetric homo/heterojunctions exhibit a weak dependence on misorientation angles, while in MoS2 both symmetric and asymmetric GBs show a gradual dependence on mismatch angles.

Probing the electronic structure at semiconductor surfaces using charge transport in nanomembranes.

The electrical properties of nanostructures are extremely sensitive to their surface condition. In very thin two-dimensional crystalline-semiconductor sheets, termed nanomembranes, the influence of the bulk is diminished, and the electrical conductance becomes exquisitely responsive to the structure of the surface and the type and density of defects there. Its understanding therefore requires a precise knowledge of the surface condition. Here we report measurements, using nanomembranes, that demonstrate direct charge transport through the π* band of the clean reconstructed Si(001) surface. We determine the charge carrier mobility in this band. These measurements, performed in ultra-high vacuum to create a truly clean surface, lay the foundation for a quantitative understanding of the role of extended or localized surface states, created by surface structure, defects or adsorbed atoms/molecules, in modifying charge transport through semiconductor nanostructures.